EP0981574A1 - Graphitpartikel enthaltende expandierbare styrolpolymerisate - Google Patents
Graphitpartikel enthaltende expandierbare styrolpolymerisateInfo
- Publication number
- EP0981574A1 EP0981574A1 EP97923073A EP97923073A EP0981574A1 EP 0981574 A1 EP0981574 A1 EP 0981574A1 EP 97923073 A EP97923073 A EP 97923073A EP 97923073 A EP97923073 A EP 97923073A EP 0981574 A1 EP0981574 A1 EP 0981574A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- styrene polymers
- expandable styrene
- polystyrene
- weight
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002245 particle Substances 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 62
- 239000010439 graphite Substances 0.000 title claims abstract description 62
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 239000006260 foam Substances 0.000 claims abstract description 48
- 239000004793 Polystyrene Substances 0.000 claims description 41
- 229920002223 polystyrene Polymers 0.000 claims description 38
- 239000004604 Blowing Agent Substances 0.000 claims description 17
- 239000003063 flame retardant Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 7
- 150000005526 organic bromine compounds Chemical class 0.000 claims description 7
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 229920006327 polystyrene foam Polymers 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- VCNJVIWFSMCZPE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-prop-2-enoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(OCC=C)C(Br)=C1Br VCNJVIWFSMCZPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims description 2
- AUTSLLHNWAZVLE-UHFFFAOYSA-N 1,1,2,2,3-pentabromo-3-chlorocyclohexane Chemical compound ClC1(Br)CCCC(Br)(Br)C1(Br)Br AUTSLLHNWAZVLE-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000003380 propellant Substances 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- 239000011324 bead Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004794 expanded polystyrene Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 208000001848 dysentery Diseases 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011049 pearl Substances 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- -1 bromine compound Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 229920006248 expandable polystyrene Polymers 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/027—Lightweight materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/907—Nonurethane flameproofed cellular product
Definitions
- the invention relates to particulate expandable styrene polymers in particle form containing graphite particles, their preparation and foams produced therefrom.
- Polystyrene particle foams have been known for a long time and have been retained in many areas. Such foams are produced by foaming polystyrene particles impregnated with blowing agents and the subsequent welding of the foam particles thus produced to shaped bodies. An important area of application is thermal insulation in construction.
- the foams be self-extinguishing. It is known that this can be done by adding flame retardants, e.g. of bromine compounds can be achieved; However, whether a foam passes a certain fire test depends on various factors, such as the composition and density of the foam, the type and amount of flame retardant, and the type and amount of other additives.
- flame retardants e.g. of bromine compounds
- the foam panels made of polystyrene particle foam used for thermal insulation mostly have densities of at least 30 g / 1, since the thermal conductivity of the polystyrene particle foam is at a minimum at these densities.
- foam boards with lower densities especially ⁇ . 15 g / 1, to be used for heat insulation.
- the production of such foams is technically not a problem.
- Sc aumstoffplatten with lower density however, have a drastically deteriorated thermal insulation, so that they do not meet the requirements of thermal conductivity class 035 (DIN 18 164, Part 1).
- EP-A 372 343 describes polystyrene foams which contain 1 to 25% by weight of carbon black.
- the carbon black has a particle size of 10 to 100 nm and a surface of 10 to 1500 m-Vg.
- the polystyrene foams described there are predominantly produced by the extrusion process and preferably have a density of 32-40 g / 1, as is typical for these foams, on.
- the addition of flame retardants is mentioned;
- the polystyrene particle foams described in the examples with a content of 1.7% by weight of hexabromocyclododecane fail the fire test B2 according to DIN 4102).
- EP-A 620 246 describes moldings made of polystyrene particle foam which contain a particulate, athermanous material, in particular carbon black, but also graphite.
- the density of the molded body is less than 20 g / 1.
- the particles are preferably incorporated into the shaped bodies by surface coating the pre-expanded polystyrene beads or by embedding them in the not yet expanded polystyrene granules.
- this distribution of the particles on the surface leads to a severe deterioration in the welding of the pre-foamed beads and consequently to less good foams, and abrasion from the surface of the molded body can also occur.
- the particles are in any case not homogeneously distributed inside the polystyrene particles; the addition of flame retardants is not described.
- GB-A 1 588 314 describes a similar process, according to which antistatic polystyrene foams are produced by coating unfoamed or pre-foamed particles with a graphite suspension.
- the object of the invention was to provide expandable styrene polymers containing graphite particles which can be processed into polystyrene particle foams both with low density and with low thermal conductivity and which have good processing properties, good physical properties and in particular very good fire protection properties.
- particulate, expandable styrene polymers which contain graphite particles in a homogeneous distribution and can be processed into foams with a density of ⁇ 35 g / 1, which are preferably self-extinguishing and pass fire test B2 (according to DIN 4102).
- the invention furthermore relates to processes for producing the expandable styrene polymers and the polystyrene particle foams produced from them.
- Expandable styrene polymers are understood to mean styrene polymers containing blowing agents.
- the expandable styrene polymers according to the invention contain, as polymer matrix, in particular homopolystyrene or styrene copolymers with up to 20% by weight, based on the weight of the polymers, of ethylenically unsaturated comonomers, in particular alkylstyrenes, divinylbenzene, acrylonitrile or ⁇ -methylstyrene.
- Blends made of polystyrene and other polymers, in particular with rubber and polyphenylene ether, are also possible.
- the styrene polymers can contain the customary and known auxiliaries and additives, for example flame retardants, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, pigments and antioxidants.
- auxiliaries and additives for example flame retardants, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, pigments and antioxidants.
- the expandable particles are coated with the customary and known coating agents, for example metal stearates, glycerol esters and finely divided silicates.
- coating agents for example metal stearates, glycerol esters and finely divided silicates.
- the particle size is preferably in the range of 0.2-2 mm.
- the graphite used preferably has an average particle size of 1 to 50 ⁇ m, in particular 2.5 to 12 ⁇ m, a bulk density of 100 to 500 g / 1 and a specific surface area of 5 to 20 ⁇ m / g.
- Natural graphite or ground synthetic graphite can be used.
- the graphite particles are preferably contained in the styrene polymer in amounts of 0.05 to 25% by weight, in particular 2 to 8% by weight. Surprisingly, it has been shown that graphite particles are effective even in amounts of less than 0.5% by weight.
- the expandable styrene polymers are added with flame retardants, in particular those based on organic bromine compounds.
- the bromine compound (without synergist) should be added in an amount of more than 3% by weight, based on the weight of the expandable styrene polymers. Bl and B2 are missed with the usual amount of flame retardants.
- the organic bromine compounds should have a bromine content of> 70% by weight.
- this amount of flame retardants does not impair the mechanical properties of the polystyrene particle foams containing carbon black.
- Aliphatic, cycloaliphatic and aromatic bromine compounds such as hexabromocyclododecane, pentabromomochlorocyclohexane, pentabromophenyl allyl ether, are particularly suitable.
- the effect of the bromine-containing flame retardants is considerably improved by adding C-C or O-O-labile organic compounds.
- suitable flame retardant synergists are dicumyl and dicumyl peroxide.
- a preferred combination consists of 0.6 to 5% by weight of organic bromine compound and 0.1 to 1.0% by weight of the C-C or O-O-unstable organic compound.
- the expandable styrene polymers according to the invention can be prepared by various processes.
- the graphite particles are mixed with a melt of the styrene polymer, preferably in an extruder.
- the blowing agent is metered into the melt.
- the graphite particles can also be incorporated into a melt of blowing agent-containing styrene polymer, expediently using screened fractions of a bead spectrum of blowing agent-containing polystyrene beads formed in a suspension polymerization.
- the polystyrene melt containing the blowing agent and graphite particles is pressed out and comminuted into granules containing blowing agent.
- graphite has cooled quickly after pressing under pressure to avoid foaming. It is therefore expedient to carry out underwater pelletizing under pressure.
- blowing agent to the styrene polymers containing graphite particles in a separate process step.
- the granules are then preferably impregnated with the blowing agent in aqueous suspension.
- the fine-particle graphite particles can be added directly to the polystyrene melt.
- the graphite particles can also be added to the melt in the form of a concentrate in polystyrene.
- polystyrene granules and graphite Enter the particles together in an extruder, melt the polystyrene and mix it with the graphite.
- the graphite particles in the course of the suspension polymerization. They can be added to the monomeric styrene before the suspension or can be added to the reaction mixture in the course, preferably during the first half, of the polymerization cycle.
- the blowing agent is preferably added in the course of the polymerization, but it can also be incorporated into the styrene polymer afterwards. It has been shown that it is favorable for the stability of the suspension if a solution of polystyrene (or a corresponding styrene copolymer) in styrene (or the mixture of styrene with comonomers) is present at the start of the suspension polymerization.
- a 0.5 to 30, in particular 5 to 20% by weight solution of polystyrene in styrene is preferably used. It is possible to dissolve fresh polystyrene in monomers, but expediently so-called fractions are used, which are sieved out as beads which are too large or too small when the expandable polystyrene is produced, and in practice such fractions which cannot be used have such fractions Diameters greater than 2.0 mm or less than 0.2 mm. Recycled polystyrene and recycled foam polystyrene can also be used. Another possibility is to prepolymerize styrene in bulk up to a conversion of 0.5 to 70% and to suspend and prepolymerize the prepolymer together with the graphite particles in the water phase.
- the blowing agent is in the usual amounts of about
- Aliphatic hydrocarbons having 3 to 10, preferably 4 to 6, carbon atoms are usually used as blowing agents.
- the expandable, carbon black-containing styrene polymers according to the invention can be processed into polystyrene foams with densities of 5-35 g / 1, preferably 8 to 25 g / 1 and in particular 10-15 g / 1.
- the expandable particles are pre-foamed. This is usually done by heating the particles with water vapor in so-called previewers. The pre-foamed particles are then welded to form bodies. For this purpose, the pre-foamed "" particles are brought into non-gas-tight molds and water vapor is applied. After cooling, the molded parts can be removed.
- Another surprising effect of the addition of graphite particles is that the cooling time when demolding welded foam blocks can be reduced. For example, an addition of 0.5 to 5% by weight of graphite leads to a reduction in the cooling time of 10 to 90%.
- the foams produced from the expandable styrene polymers according to the invention are notable for excellent thermal insulation. This effect is particularly evident at low densities.
- the thermal conductivity could be reduced from 44 mW / m-K to below 35 mW / mK.
- Another object of the invention are polystyrene particle foams with a density of ⁇ 35 g / 1, which contain 0.05 to 25% by weight of graphite particles in a homogeneous distribution, the thermal conductivity of which is reduced to such an extent that they meet the requirements of thermal conductivity class 035 (according to DIN 18 164, Part 1, Table 4), which are preferably self-extinguishing and meet fire test B2 (according to DIN 4102).
- the expandable styrene polymers according to the invention can be processed into foams of low density without any problems. There is no loss of blowing agent or disturbances in the cell structure of the foams, although the person skilled in the art had to assume that the graphite acts as a nucleating agent and would lead to an undesirable fine cell structure of the foam and poor welding. In addition, despite the addition of graphite particles, self-extinguishing foams can be produced that pass fire test B2 and in most cases also B1. Due to the integration of the graphite particles in the polymer matrix there is no abrasion of the graphite and "" therefore no contamination when working with such components.
- the foams according to the invention can be used for the thermal insulation of buildings and parts of buildings, for the thermal insulation of machines and household appliances and as packaging materials.
- EPS fractions are dissolved in 16.6 kg styrene and 16.6 g powdered graphite (Graphitwerk Kropfmuhl KG, UF2 96/97), i.e. 0.1% graphite, based on the total amount of styrene and EPS, homogeneously suspended with the addition of 83.0 dicumyl peroxide and 4.15 g dibenzoyl peroxide, and 112.033 g hexabromocyclododecane (HBCD).
- the organic phase is introduced into 19.3 l of completely demineralized water in a 50 l Ruhr kettle.
- the aqueous phase contains 46.127 g of sodium pyrophosphate and 86.348 g of magnesium sulfate (Epsom salt).
- the suspension is heated to 80 ° C. within 140 minutes.
- 2.32 g of emulsifier K 30/40 (Bayer AG) are added.
- 1330 g of pentane are metered in and polymerized at 126 ° C.
- Example 1 was repeated without adding graphite.
- the coefficient of thermal conductivity at a density of 10 g / 1 was 44 mW / mK.
- Example 3
- HBCD hexabromocyclododecane
- the mixture was then stirred at 90 ° C. for a further 2 hours and 7 parts of a mixture of 80% n-pentane and 20% iso-pentane were added. 5 The mixture was then stirred at 110 ° C. for 2 hours and finally at 140 ° C. for 2 hours.
- the expandable polystyrene beads obtained were washed with deionized water and sieved to 0.7-1.0 mm and then dried with warm air.
- the beads were pre-foamed by the action of flowing water vapor and after storage for one day by further treatment with steam in a closed mold they were welded into foam blocks with a density of 15 g / l.
- the measurement of the coefficient of thermal conductivity was carried out at 10 n C according to DIN 52612. The result was a value of 34 mW / mK.
- the pearls can be used
- Example 4 was repeated with 4% graphite.
- Example 4 was repeated with t 2% graphite
- Example 4 was repeated with 1% graphite.
- Example 4 was repeated with 0.5% graphite.
- Example 4 was repeated with 0.2% graphite.
- Example 4 was carried out without the addition of graphite.
- Example 4 was repeated, 127 g of hexabromocyclododecane and 85 g of dicumyl being added as the flame retardant system.
- the polymerization was carried out at 125 ° C. There was one Thermal conductivity of 34 mW / mK. Fire protection class B 2 was achieved.
- Polystyrene with an average molecular weight (M w ) of 220,000 (PS 148 H BASF) and a content of 2.1% HBCD and 0.42% dicumyl was added as a 20% batch in polystyrene with the addition of the amounts of graphite given in Table 1 plasticized in a heated twin-screw extruder at 180 C and pressed through a die plate of 1 mm in diameter. The strands were solidified in a water bath and then granulated to a particle size of 2x2x2 mm using rotating knives.
- Example 15 foaming to a density of 10.3 g / 1, in Example 16 (with a shorter evaporation time) to a density of 15 g / 1.
- the thermal conductivities were 34 and 32 mW / m-K. The B2 test was passed in each case.
- the coefficient of thermal conductivity was 34 and 44 mW / m-K. The B2 test was not passed in each case.
- Polystyrene PS 158 K (BASF AG) was metered together with 2% graphite, 1.4% HBCD and 0.7% dicumyl in a twin-screw extruder (ZSK 53). In addition, 5% pentane was added to the melt in the extruder.
- the melt emerging from the extruder die was granulated using an underwater pelletizer from Gala (USA). The granulation was carried out under 5 bar pressure. This pressure was achieved by means of a throttle (hose with a length of 50 m) which was installed between the granulation and dryer. Pearl-shaped black granules with an average diameter of about 1.5 mm were obtained. Moldings produced by foaming and sintering the foam particles had a thermal conductivity of 35 mW / m-K at a density of 13 g / 1.
- Pre-expanded EPS beads were mixed with 2.0% graphite in a mixing unit. An incomplete coating and uneven distribution of the graphite on the surface of the pearls were found. A strong abrasion of the graphite from the pearl surface was observed during further processing. The use of binders (glycerin stearate, white oil) did not improve the quality of the coating results. The welding of the molded parts was unsatisfactory.
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Description
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/EP1997/002458 WO1998051735A1 (de) | 1997-05-14 | 1997-05-14 | Graphitpartikel enthaltende expandierbare styrolpolymerisate |
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EP0981574A1 true EP0981574A1 (de) | 2000-03-01 |
EP0981574B1 EP0981574B1 (de) | 2000-09-06 |
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US (1) | US6340713B1 (de) |
EP (1) | EP0981574B1 (de) |
JP (1) | JP4324250B2 (de) |
AT (1) | ATE196158T1 (de) |
AU (1) | AU2897997A (de) |
DE (1) | DE59702327D1 (de) |
ES (1) | ES2151268T3 (de) |
WO (1) | WO1998051735A1 (de) |
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Also Published As
Publication number | Publication date |
---|---|
JP2001525001A (ja) | 2001-12-04 |
JP4324250B2 (ja) | 2009-09-02 |
DE59702327D1 (de) | 2000-10-12 |
US6340713B1 (en) | 2002-01-22 |
WO1998051735A1 (de) | 1998-11-19 |
EP0981574B1 (de) | 2000-09-06 |
ES2151268T3 (es) | 2000-12-16 |
AU2897997A (en) | 1998-12-08 |
ATE196158T1 (de) | 2000-09-15 |
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